CN101341584A - Method for modifying highly dielectric thin film and semiconductor device - Google Patents

Method for modifying highly dielectric thin film and semiconductor device Download PDF

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Publication number
CN101341584A
CN101341584A CNA2006800483123A CN200680048312A CN101341584A CN 101341584 A CN101341584 A CN 101341584A CN A2006800483123 A CNA2006800483123 A CN A2006800483123A CN 200680048312 A CN200680048312 A CN 200680048312A CN 101341584 A CN101341584 A CN 101341584A
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thin film
dielectric thin
highly dielectric
modifying
oxygen
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CN101341584B (en
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山崎和良
青山真太郎
秋山浩二
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Abstract

This invention provides a method for modifying a highly dielectric thin film provided on the surface of an object using an organometallic compound material, and a semiconductor device. The method comprises a provision step of providing the object with the highly dielectric thin film formed on the surface thereof, and a modification step of applying ultraviolet light to the highly dielectric thin film in an inert gas atmosphere while maintaining the object at a predetermined temperature to modify the highly dielectric thin film. According to the above constitution, the carbon component can be eliminated from the highly dielectric thin film, and the whole material can be thermally shrunk to improve the density, whereby the occurrence of defects can be prevented and the film density can be improved to enhance the specific permittivity and thus to provide a high level of electric properties.

Description

The method of modifying of highly dielectric thin film and semiconductor device
Technical field
The present invention relates to the method for modifying of the highly dielectric thin film that on the surface of handled objects such as semiconductor wafer, forms and use the semiconductor device of the gate insulating film that obtains by this modification.
Background technology
Usually, when making semiconductor integrated circuit, to handled objects such as semiconductor wafers, one piece of one piece of ground repeats various processing such as film forming processing, etch processes, heat treatment, modification processing, crystallization processing, forms the semiconductor integrated circuit of expectation.
In recent years, about such integrated circuit, owing to further require the high speed of the responsiveness of this integrated circuit, highly integrated and filming, miniaturizations more such as the live width in the integrated circuit, thickness.Here be example with transistor as the semiconductor device of semiconductor integrated circuit, then since the requirement of above-mentioned miniaturization must make the thickness that is arranged on the gate insulating film on this transistor thinner, and make the length of this gate insulating film shorter.Particularly, need be 1～2nm or below it with the thickness setting of gate insulating film, but tunnel current increase in so extremely thin gate insulating film, consequently, grid leakage current increases.
Therefore, there is replacement SiO 2Film will be far longer than SiO as dielectric constant 2The highly dielectric thin film of the film of the high dielectric property of film is as the tendency (for example with reference to TOHKEMY 2002-100627 communique, Japanese kokai publication hei 10-135233 communique etc.) of the main body of gate insulating film.As such highly dielectric thin film, for example can enumerate HfO 2, HfSiO 2, ZrO 2, ZrSiO 4Oxide Deng the refractory metal material.
Such highly dielectric thin film is formed directly on silicon substrate or the silicon fiml, and under the situation as the gate insulating film use, metallic atom is diffused into silicon substrate or the silicon fiml from this highly dielectric thin film, and the scattering of charge carrier takes place in raceway groove (channel) zone.Therefore, in order to prevent the diffusion of metallic atom,, form extremely thin for example counting in the lower floor of this highly dielectric thin film
Figure A20068004831200051
(
Figure A20068004831200052
) about SiO 2Film is as basilar memebrane.Than with this SiO 2Film is as the 1～2nm for example of the thickness under the situation of gate insulating film, as the SiO of this basilar memebrane 2Film will approach a lot.With reference to Figure 15, to describing as a transistorized example with semiconductor device of such grid structure.Figure 15 is that expression is with the summary construction diagram of highly dielectric thin film as a transistorized example of gate insulating film.
In Figure 15, on the surface of the semiconductor wafer W that constitutes by silicon substrate etc., be formed with source S and drain D, on the surface between this source S and the drain D, becoming successively, lamination has by SiO 2The structure of basilar memebrane 2, highly dielectric thin film 4, nitride film 6 and gate electrode 8 that film constitutes.Above-mentioned basilar memebrane 2 for example carries out oxidation processes by the silicon face to semiconductor wafer W and forms.Above-mentioned highly dielectric thin film 4 will comprise the organo-metallic compound material of refractory metal such as Hf as raw material, by hot CVD (Chemical Vapor Deposition: chemical vapour deposition (CVD)) handle and form.
Above-mentioned nitride film 6 forms by nitrogen treatment is carried out on the surface of above-mentioned highly dielectric thin film 4, and this nitride film 6 has the effect that the metal material that prevents in the gate electrode 8 spreads in highly dielectric thin film 4.As above-mentioned gate electrode 8, for example can use the polysilicon film that is injected with impurity, metal films such as tungsten, tantalum, or its nitride film etc.
But, under the situation that forms aforesaid highly dielectric thin film 4, because use the organo-metallic compound material, so can't avoid carbon (C) composition of the amount to a certain degree of in this film, sneaking into.So this carbon component of sneaking into reduces dielectric constant, produces leakage current, and then becomes the unsettled reason of transistorized threshold value.Therefore, after forming highly dielectric thin film 4, under the high temperature about 800～1000 ℃, carry out annealing in process, to remove above-mentioned carbon component of sneaking into as much as possible.
But under the situation of the annealing in process of carrying out high temperature like this, the part that carbon component breaks away from produces damaged, is descended by this damaged film density reduction, dielectric constant of causing, and therefore has membranous deterioration, can not obtain the problem of the electrical characteristics of target.
As the damaged method of repairing in such highly dielectric thin film, the known in the prior art oxygen radical that plasma has been encouraged is exposed to the method on the highly dielectric thin film, perhaps in ozone gas atmosphere to the method (UV-O of highly dielectric thin film irradiation ultraviolet radiation 3Handle) (for example with reference to Japanese kokai publication hei 9-121035 communique).
But have following problems in the oxygen radical that plasma has been encouraged is exposed to method on the highly dielectric thin film: generate the free radical of unmanageable surplus, this free radical is by highly dielectric thin film, makes the SiO of basilar memebrane 2Thickness increases, thereby makes EOT (the Equivalent Oxide Thickness: equivalent oxide thickness) increase of gate insulating film.Wherein, EOT is the SiO with lamination highly dielectric thin film and basilar memebrane 2Film and the electric capacity of the gate insulating film that forms is converted into single S iO 2The resulting value of thickness.
In addition, at above-mentioned UV-O 3Also there is following problem in the method for handling: because use ozone, so the oxygen in repairing highly dielectric thin film also causes the SiO of basilar memebrane in damaged as potent oxidant 2The increase of thickness makes the EOT of gate insulating film increase.
Summary of the invention
The present invention proposes in view of the above problems.The method of modifying and the semiconductor device that the purpose of this invention is to provide a kind of highly dielectric thin film, relative highly dielectric thin film, by irradiation ultraviolet radiation under the temperature of regulation, in non-active gas atmosphere or in the oxygen atmosphere, implement modification and handle, from highly dielectric thin film, remove carbon component, and make integral heat pressure cooperate (baked I Parties あ), improve density, can prevent damaged generation thus, and can improve film density, thereby can improve dielectric constant, obtain higher electrical characteristics.
A mode of the present invention is, a kind of method of modifying of highly dielectric thin film, the method of modifying of the highly dielectric thin film that be to use the organo-metallic compound material, on the surface of handled object, forms, it is characterized in that, comprising: preparation is formed with the preparatory process of the above-mentioned handled object of above-mentioned highly dielectric thin film from the teeth outwards; With keep above-mentioned handled object the regulation temperature, and in the atmosphere of non-active gas to above-mentioned highly dielectric thin film irradiation ultraviolet radiation, carry out the modified process of the modification of above-mentioned highly dielectric thin film thus.
Like this, by at low temperatures, in non-active gas atmosphere relative highly dielectric thin film irradiation ultraviolet radiation, carry out modified process, from highly dielectric thin film, remove carbon component, and the handled object integral heat pressure is cooperated, improve density, can prevent damaged generation thus, and the raising film density, thereby improve dielectric constant, can access higher electrical characteristics.
In this case, the method of modifying of highly dielectric thin film can also comprise and reoxidizes operation, it is the operation of carrying out before being about to carry out above-mentioned modified process, keep the temperature of above-mentioned handled object in regulation, and in the atmosphere of oxygen to above-mentioned highly dielectric thin film irradiation ultraviolet radiation, the oxygen of repairing thus in the above-mentioned highly dielectric thin film is damaged.
In this case, because the oxygen that can repair in the highly dielectric thin film is damaged, so can correspondingly improve membranous.
Perhaps, the method of modifying of highly dielectric thin film can also comprise and reoxidizes operation, it is the operation that and then above-mentioned modified process carries out, keep the temperature of above-mentioned handled object in regulation, and in the atmosphere of oxygen to above-mentioned highly dielectric thin film irradiation ultraviolet radiation, the oxygen of repairing thus in the above-mentioned highly dielectric thin film is damaged.
In this case, because the oxygen that can repair in the highly dielectric thin film is damaged, so can correspondingly improve membranous.
Another way of the present invention is, a kind of method of modifying of highly dielectric thin film, the method of modifying of the highly dielectric thin film that be to use the organo-metallic compound material, on the surface of handled object, forms, it is characterized in that, comprising: preparation is formed with the preparatory process of the above-mentioned handled object of above-mentioned highly dielectric thin film from the teeth outwards; With keep above-mentioned handled object the regulation temperature, and in the atmosphere of oxygen to above-mentioned highly dielectric thin film irradiation ultraviolet radiation, carry out the modified process of the modification of above-mentioned highly dielectric thin film thus.
Like this, by relative highly dielectric thin film irradiation ultraviolet radiation under the temperature of regulation, in oxygen atmosphere, carry out modified process, from highly dielectric thin film, remove carbon component, and integral heat pressure is cooperated, improve density, can prevent damaged generation thus, and the raising film density, thereby improve dielectric constant, can access higher electrical characteristics.
Herein, in the atmosphere of above-mentioned oxygen to the processing pressure of the operation of above-mentioned highly dielectric thin film irradiation ultraviolet radiation preferably in the scope of 2.6～65Pa.
In addition, above-mentioned ultraviolet ray preferably wavelength based on the ultraviolet ray of 172mm.
In addition, preferably in the lower floor of above-mentioned highly dielectric thin film, be formed with by the SiO that forms by oxidation processes 2The basilar memebrane that film constitutes.
Herein, above-mentioned basilar memebrane preferably forms in the basilar memebrane formation operation of carrying out before the operation by the highly dielectric thin film that forms above-mentioned highly dielectric thin film on the surface of handled object and forms.
Perhaps, above-mentioned basilar memebrane forms when carrying out above-mentioned modified process simultaneously.
In addition, the temperature of the regulation in the above-mentioned modified process is preferably the temperature of the oxygen key (oxygen bond) that does not cut off above-mentioned highly dielectric thin film.The temperature of the regulation in the above-mentioned modified process especially is preferably below 500 ℃.
In addition, above-mentioned highly dielectric thin film preferably is made of the oxide of refractory metal or the silicate of this oxide.
In addition, above-mentioned refractory metal is preferably any among Hf, Ta, Ti, W, the Zr.
In addition, preferably after above-mentioned modified process, be used for the nitrogenize operation on the surface of the above-mentioned highly dielectric thin film of nitrogenize.
Perhaps, preferably before above-mentioned modified process, be used for the nitrogenize operation on the surface of the above-mentioned highly dielectric thin film of nitrogenize.
In addition, preferred above-mentioned highly dielectric thin film is transistorized gate insulating film.
In addition, preferred above-mentioned non-active gas is N 2, among He, Ar, Ne, Kr, the Xe arbitrarily more than one.
Another mode of the present invention is that a kind of semiconductor device is characterized in that: comprise that the highly dielectric thin film that is modified by above-mentioned method of modifying is as gate insulating film.
According to the method for modifying and the semiconductor device of highly dielectric thin film of the present invention, can bring into play the action effect of excellence as described below.
According to the present invention, by relative highly dielectric thin film irradiation ultraviolet radiation under the temperature of regulation, in non-active gas atmosphere or in the oxygen atmosphere, carry out modified process, from highly dielectric thin film, remove carbon component, and integral heat pressure is cooperated, improve density, can prevent damaged generation thus, and the raising film density, thereby can improve dielectric constant, obtain higher electrical characteristics.
Description of drawings
Fig. 1 is the summary construction diagram of an example of the expression treatment system that is used to implement the inventive method.
Fig. 2 is the figure that is illustrated in the general structure of the apparatus for ultraviolet light treamtent that uses in the treatment system.
Fig. 3 is the flow chart of operation of first embodiment of expression the inventive method.
Fig. 4 A is the chart of the relation of expression ultraviolet irradiation time and thickness.
Fig. 4 B is the chart that the concentration of carbon on the depth direction of expression thickness distributes.
Fig. 5 is the flow chart of operation of second embodiment of expression the inventive method.
Fig. 6 is the flow chart of operation of the 3rd embodiment of expression the inventive method.
Fig. 7 is the flow chart of operation of the 4th embodiment of expression the inventive method.
Fig. 8 is the flow chart of operation of the 5th embodiment of expression the inventive method.
Fig. 9 is the flow chart of operation of the 6th embodiment of expression the inventive method.
Figure 10 is expression ultraviolet irradiation and the atmosphere gas chart to the influence of the concentration of carbon of highly dielectric thin film.
Figure 11 is the flow chart of operation of the 7th embodiment of expression the inventive method.
Figure 12 is the chart of the relation of expression EOT and grid leakage current.
Figure 13 A is expression UV-O 2Handle (wavelength: 172nm) and the chart of the relation of EOT.
Figure 13 B is expression UV-O 2Handle (wavelength: 172nm) and the chart of the relation of trap (trap) density.
Figure 14 is expression UV-O 2The chart of the relation of middle flat band voltages (Vfb) such as processing, UV-Ar handle and trap density.
Figure 15 is that expression is with the summary construction diagram of highly dielectric thin film as a transistorized example of gate insulating film.
Embodiment
Below, with reference to accompanying drawing the method for modifying of highly dielectric thin film of the present invention and an embodiment of semiconductor device are elaborated.
Fig. 1 is the summary construction diagram of an example of the expression treatment system that is used to implement the inventive method, and Fig. 2 is the figure that is illustrated in the general structure of the apparatus for ultraviolet light treamtent that uses in the above-mentioned treatment system.
At first, with reference to Fig. 1, the treatment system that comprises the apparatus for ultraviolet light treamtent (reforming apparatus) of implementing the inventive method is described.
As shown in Figure 1, treatment system 12 the trooping of quilt to handling as the semiconductor wafer that for example is made of silicon substrate of handled object mainly comprise: for example be the shared carrying room 14 of octagonal shape; Be arranged on six processing unit 16A, 16B, 16C, 16D, 16E, the 16F of the periphery of this shared carrying room 14; With two load locking room 18A, 18B.Between above-mentioned shared carrying room 14 and each processing unit 16A～16F and each load locking room 18A, 18B, be respectively arranged with can switch gate valve G, and take out of side moving into of each load locking room 18A, 18B and also be provided with identical gate valve G.
Above-mentioned two load locking room 18A, 18B can be evacuated and recover atmospheric pressure.Will be when recovering atmospheric pressure as for example N of non-active gas 2Gas is full of in this load locking room 18A, the 18B.
By this load locking room 18A, 18B, in the outside of atmospheric pressure side and become between the above-mentioned shared carrying room 14 of vacuum atmosphere and move into and take out of wafer W.
In the above-mentioned shared carrying room 14, when work, be generally vacuum atmosphere.And, in shared carrying room 14, be provided with two transport mechanisms 20 that pick up type that can rotate,, can between above-mentioned each processing unit 16A～16F and each load locking room 18A, 18B, freely move into and take out of wafer W by making the action of this transport mechanism 20 with flexor.
Then each processing unit is described.
At first, first processing unit 16A is the pretreating device that carries out pre-treatment.In this pretreating device 16A, use nitrogen free radical, hydroperoxyl radical and NF 3Gas etc. are with the natural oxide (SiO of wafer surface 2) be transformed to the volatility film of N-O-Si-H class, and be removed.
Second processing unit 16B is that the substrate that is used to form extremely thin basilar memebrane 2 (with reference to Figure 15) becomes membrane treatment appts.Become among the membrane treatment appts 16B in this substrate, utilize the oxygen radical oxidation wafer surface of under low pressure using ultraviolet ray (below be also referred to as " UV ") and oxygen and producing, form by SiO thus 2The above-mentioned basilar memebrane 2 that film constitutes, this is a kind of of apparatus for ultraviolet light treamtent.And, as described later,, also exist and do not use this substrate to become the situation of membrane treatment appts 16B according to the mode of embodiment.
The 3rd processing unit 16C is the CVD processing unit that is used to form highly dielectric thin film 4 (with reference to Figure 15).In this CVD processing unit 16C, use the organo-metallic compound material, form HfSiO by hot CVD 2Deng highly dielectric thin film 4.As previously mentioned, because in film forming is handled, use the organo-metallic compound material, so in this highly dielectric thin film 4, comprise carbon.
The 4th processing unit 16D is the processing unit that reoxidizes that is used to reoxidize operation.Reoxidize among the processing unit 16D at this, the oxygen radical that uses ultraviolet ray and oxygen and produce is exposed to wafer surface, the reparations that oxygen in the film that carries out thus forming on wafer surface is damaged etc., this reoxidizes processing unit 16D is a kind of of apparatus for ultraviolet light treamtent.And, as described later,, also there is the situation that this reoxidizes processing of not carrying out according to the mode of embodiment, perhaps change the situation of the order of carrying out.
The 5th processing unit 16E is the modification processing unit that carries out the modified process of above-mentioned highly dielectric thin film 4.In this modification processing unit 16E, for example under the low temperature below 500 ℃, above-mentioned highly dielectric thin film 4 is exposed to ultraviolet ray and non-active gas, or ultraviolet ray and O 2In the gas, thereby carry out modification, carbon component is broken away from from film, and make the film shrink fit, improve its density.
The a series of modification action of above-mentioned relatively highly dielectric thin film 4 is meant: the situation of the independent modified process that is undertaken by this modification processing unit 16E and merge and carry out this modified process and by the previous situation that reoxidizes these two operations of operation that processing unit carries out that reoxidizes.This modification processing unit 16E is a kind of of apparatus for ultraviolet light treamtent.
And, as described later, in this modified process,, there is the situation of using ultraviolet ray and non-active gas according to the mode of embodiment, and the situation of using ultraviolet ray and oxygen.
The 6th processing unit 16F is the nitrogen treatment device that is used to form the nitrogen treatment of nitride film 6 (with reference to Figure 15).In this nitrogen treatment device 16F, at N 2Gas, NH 3Under the existence of gas, use plasma that nitrogen treatment is carried out on the surface of highly dielectric thin film 4, form nitride films 6 such as SiN thus.And, as described later,, also there is the situation of not carrying out this nitrogenize operation, or changes the situation of the order of carrying out according to the mode of embodiment.
In addition, under the situation that above-mentioned each processing unit 16A～16F is not used according to the mode of embodiment described later, this obsolete device is not set certainly.
Then, the structure that becomes membrane treatment appts 16B in above-mentioned substrate, reoxidizes apparatus for ultraviolet light treamtent common in each processing unit of processing unit 16D and modification processing unit 16E is described.
This apparatus for ultraviolet light treamtent 22 (common structure in each device of 16B, 16D, 16E) for example has the cylinder-shaped container handling 24 of aluminum that can vacuum exhaust.In this container handling 24, be provided with and be used for the mounting table 26 of mounting semiconductor wafer W in the above, in this mounting table 26, be embedded with the resistance heater 28 that is used to heat above-mentioned wafer W.Below central portion below this mounting table 26 is connected with and extends to, inside forms the swinging strut 30 of hollow sealed shape, this swinging strut 30 inserts and also connects the through hole 32 that is arranged on the container bottom 24A.And, in this through hole 32, inserting and be provided with magnetic fluid seal spare 34, it maintains airtight sealing state in above-mentioned container handling 24 in the rotation that allows above-mentioned swinging strut 30, and supports this swinging strut 30.
Be provided with gear mechanism 36 in the bottom of this swinging strut 30, drive this gear mechanism 36, above-mentioned swinging strut 30 and mounting table 26 are rotated integratedly by motor 38.In addition, in the swinging strut 30 of this hollow form, be equipped with the supply lines 40 that is connected with above-mentioned resistance heater 28, the lower end of this supply lines 40 is connected with the collector ring (slip ring) 42 of the bottom that is arranged on swinging strut 30, powers from the outside.
The bottom 24A of above-mentioned container handling 24 is provided with exhaust outlet 44, on this exhaust outlet 44, be connected with the exhaust channel 50 that is provided with pressure-regulating valve 46, vacuum pump 48 etc. on the way, as required, can will be maintained the pressure of regulation in the above-mentioned container handling 24 and vacuumize.
In addition, on the 24B of the top of this container handling 24, be formed with elongated irradiation hole 52, and on this irradiation hole 52, the penetrating window 54 with ultraviolet relatively permeability be installed airtightly by seal members 56 such as O shape circles.And, in the arranged outside of this penetrating window 54 ultra-violet lamp 58 is arranged, by above-mentioned penetrating window 54, can be to the surface irradiation ultraviolet ray of the wafer W of rotation status.
In addition, the sidewall of container handling 24 be provided with can switch gate valve G, can take out of wafer W moving between itself and the shared carrying room 14 by open gate valve G.
In addition, on the container side wall of the opposition side of the installation site of above-mentioned gate valve G, for example be provided with gas nozzle 60 as gas introduction unit, can with needed gas control flow feed in the container handling 24.The gas supplied here is oxygen at substrate film formation device 16B with reoxidizing under the situation about using among the processing unit 16D.In addition, under the situation about in modification processing unit 16E, using, carrying out ultraviolet ray-oxygen (UV-O 2) supply with oxygen when handling, carrying out supplying with non-active gas when ultraviolet ray-non-active gas (UV-is nonactive) is handled.As non-active gas, can use N herein, 2, any one or more mist among He, Ar, Ne, Ke, the Xe, the example among the figure represents to use the situation of Ar gas.
Under the situation about handling in such apparatus for ultraviolet light treamtent 22, mounting wafer W on mounting table 26 makes this wafer W maintain the temperature of regulation by resistance heater 28, rotates the integral body of mounting table 26 simultaneously.And, in container handling 24, supply with the gas corresponding, for example O with processing mode 2Gas or Ar gas (non-active gas) will maintain the pressure of regulation in the container handling 24.Meanwhile, make ultra-violet lamp 58 work,, carry out predetermined process by the surface irradiation ultraviolet ray of the wafer W of penetrating window 54 in rotation.Herein, as ultraviolet ray, which type of wavelength all is fine, but as representational wavelength, can use radiation with the ultraviolet ultra-violet lamp of each wavelength such as 172nm, 183nm, 258nm, preferably use radiation with the wavelength of 172nm ultraviolet excited quasi-molecular lampbulb as the wavelength of main body as the wavelength of main body.
And, because above-mentioned substrate film formation device 16B, to reoxidize processing unit 16D and modification processing unit 16E structure as noted above identical respectively, so one or two apparatus for ultraviolet light treamtent 22 can be set, the gaseous species that make to use is identical or change, thus carry out respectively above-mentioned each handle.
Then, the inventive method of using treatment system shown in Figure 1 12 and apparatus for ultraviolet light treamtent 22 (16B, 16D, 16E) shown in Figure 2 to carry out is described.
＜the first embodiment 〉
At first, first embodiment to the inventive method describes.
Fig. 3 is the flow chart of operation of first embodiment of expression the inventive method.At first, by any one load locking room among two load locking room 18A, the 18B (with reference to Fig. 1), be taken in the shared carrying room 14, and it is moved into pretreating device 16A, carry out pretreatment procedure (step S1) untreated semiconductor wafer W.In this pretreatment procedure, as mentioned above, use nitrogen free radical, hydroperoxyl radical and NF 3Gas etc. are removed attached to the natural oxide film on the wafer surface.
Like this,, then this wafer W is transferred load to substrate from above-mentioned pretreating device 16A and become membrane treatment appts 16B, carry out basilar memebrane and form operation (step S2) if the pretreating device processing finishes.This substrate film formation device 16B forms structure shown in Figure 2, makes to be O in the container handling 24 2Gas atmosphere makes the wafer W rotation of mounting on the mounting table 26, simultaneously from ultra-violet lamp 58 to the wafer surface irradiation ultraviolet radiation, make the wafer surface oxidation, can under the high state of inner evenness, form thus by extremely thin SiO 2The basilar memebrane 2 (with reference to Figure 15) that film constitutes.At this moment processing pressure is lower, for example is about 2.6～133Pa.In addition, treatment temperature for example is about 450～700 ℃.The target thickness of basilar memebrane 2 for example is 4
Figure A20068004831200141
About, the ultraviolet irradiation time is very short.
Like this, finish, then this wafer W is transferred load to CVD processing unit 16C from above-mentioned substrate film formation device 16B, carry out highly dielectric thin film and form operation (step S3) if basilar memebrane forms operation.Form in the operation at this highly dielectric thin film, use the organo-metallic compound material, on wafer surface, form highly dielectric thin film 4 (with reference to Figure 15) by hot CVD.
As this highly dielectric thin film 4, as mentioned above, for example the oxide (HfO), the silicate (HfSiO) of this oxide etc. of Hf (hafnium) carry out film forming to refractory metal.The thickness of this highly dielectric thin film 4 for example is 10～50
Figure A20068004831200142
About.At this moment treatment temperature is for example in 350～600 ℃ scope.In addition, processing pressure is for example in the scope of 35～400Pa.
In addition, as the above-mentioned high melting point metal materials that comprises hafnium, can use to be selected from four dimethylamino hafnium Hf[N (CH 3) 2] 4, two (cyclopentadienyl group) hafnium Hf (CH of dimethyl 3) 2(C 5H 5) 2In a kind of material.
Like this, finish, then this wafer W is transferred load to modification processing unit 16E from above-mentioned CVD film formation device 16C, carry out the modified process (step S4) of feature of the present invention if highly dielectric thin film forms operation.And, do not reoxidize processing unit 16D because use here, so skip this device.
This modification processing unit 16E forms structure shown in Figure 2, make and be for example Ar gas atmosphere in the container handling 24 as non-active gas, make the wafer W rotation of mounting on the mounting table 26, simultaneously by 58 pairs of wafer surface irradiation ultraviolet radiations of ultra-violet lamp, carry out the modification of the highly dielectric thin film 4 (with reference to Figure 15) that on wafer surface, forms and handle.
The processing pressure here is for example in the scope of 2.6～133Pa.In addition, treatment temperature is for example carried out under the temperature below 500 ℃ for not cutting off the low temperature of the oxygen key in the above-mentioned highly dielectric thin film 4.And, consider preferably treatment temperature to be set at the efficient of modification about 450 ℃.In addition, the processing time for example is about 300～1800sec also according to the thickness of highly dielectric thin film 4.
With organic components remaining in the highly dielectric thin film 4, particularly carbon component is removed by this modified process, and film carries out shrink fit and becomes firm.Consequently, the film density of highly dielectric thin film 4 improves, densification, therefore can prevent damaged generation, can keep the high-k state.
Because can improve the membranous of highly dielectric thin film 4 like this, so can make its electrical characteristics good.And, in this first embodiment, carry out the modification operation separately by modified process.
Like this,, then this wafer W is transferred load to nitrogen treatment device 16F from above-mentioned modification processing unit 16E, carry out nitrogenize operation (step S5) if modified process finishes.
In this nitrogenize operation, at N 2Gas or NH 3In the gas atmosphere, produce plasma, produce the free radical and the nitrogen free radical of above-mentioned gas kind, make this free radical act on the surface of above-mentioned highly dielectric thin film 4 and carry out nitrogenize, thereby form nitride film 6 (with reference to Figure 15).
Like this, if the nitrogenize operation finishes, then this wafer W is taken out from nitrogen treatment device 16F, and then wafer W is taken out of to the outside by load locking room, a series of processing in this treatment system 12 finishes.
Afterwards, on this wafer W, form gate electrode 8 as shown in figure 15, finishing transistor is semiconductor device.
, experimentize herein, the validity of the ultraviolet irradiation in the modified process is estimated, its evaluation result is described.
Fig. 4 is the chart of expression ultraviolet irradiation to the influence of the thickness of highly dielectric thin film and concentration of carbon.
Fig. 4 A represents the relation of ultraviolet irradiation time and thickness, and Fig. 4 B represents that the concentration of carbon on the depth direction of thickness distributes.At first, the transverse axis in the chart of Fig. 4 A is represented ultraviolet irradiation time, and the longitudinal axis is represented the variable quantity of thickness.The situation of (UV) that characteristic A among Fig. 4 A represents there is not ultraviolet irradiation, the situation of (characteristic A, B are in Ar atmosphere) that characteristic B represents that ultraviolet irradiation is arranged.In addition, the thickness setting with the highly dielectric thin film at initial stage is 40
Figure A20068004831200151
, be heated 450 ℃ and be arranged in the Ar atmosphere.Use blooming analyzer (Ellipsometer: the variation of mensuration thickness ellipsometer).
From this chart as can be known, characteristic A, B begin to about the 300sec from experiment, and thickness reduces rapidly.This is because the organic components of piling up on the surface of film mainly is that carbon component breaks away from.And, after this, do not have the thickness linearity thickening bit by bit among the characteristic A of UV irradiation.Its reason is, owing to remain in the lip-deep O of film 2Composition, H 2The O composition, the film surface is oxidized, consequently thickness thickening gradually.
Relative therewith, have UV irradiation (wavelength: characteristic B 172nm), after this, thickness once increased, but thereafter then bit by bit linearity reduce.Its reason is that highly dielectric thin film itself shines little by little shrink fit by UV, becomes fine and close, consequently thickness minimizing.Like this, can confirm irradiation, can make the highly dielectric thin film shrink fit, make its density densification by UV.In addition, measure density, thickness, the roughness (surface roughness) of highly dielectric thin film, its result is illustrated in the following table 1.Wherein, this is measured and uses XRR (X ray reflection rate method).
[table 1]
Figure A20068004831200161
From above-mentioned table 1 as can be known, about the density of film, from the 5.17g/cm of initial value 3Beginning increases under the situation that does not have the UV irradiation to a certain extent, reaches 5.16g/cm 3, relative therewith, under the situation that the UV irradiation is arranged, significantly increase to 5.38g/cm 3, can confirm that film density can significantly increase under the situation that the UV irradiation is arranged.
In addition, about thickness, from the 3.34nm of initial value, under the situation that does not have the UV irradiation only is to be thinned to 3.31nm, relative therewith, attenuation significantly under the situation that the UV irradiation is arranged, reach 3.22nm, can confirm that thickness is attenuation significantly under the situation that the UV irradiation is arranged.
In addition,, compare almost not variation, can confirm not produce any problem with initial value about roughness.
In addition, in Fig. 4 B, the state of having represented the sample test portion that is made in the drawings, on silicon substrate, thickness with 10nm forms the two-layer highly dielectric thin film that is made of HfSiO respectively, the highly dielectric thin film of lower floor carries out 30 minutes UV irradiation under Ar atmosphere, the highly dielectric thin film on upper strata does not carry out the UV irradiation.In addition, heating-up temperature is set at 450 ℃.Then, as depth direction, utilize SIMS (secondary ion mass spectrometry with halogen labeling) to measure concentration of carbon with the thickness direction of this two-layer highly dielectric thin film.X among the figure, Y are equivalent to the thickness of each layer.
From the chart shown in this Fig. 4 B as can be known, concentration of carbon is 6.0 * 10 under the situation that does not have the UV irradiation 19Atoms/cm 3, relative therewith, concentration of carbon is 1.3 * 10 under the situation that the UV irradiation is arranged 19Atoms/cm 3, reduce significantly, can confirm concentration of carbon is significantly reduced by the UV irradiation.
＜the second embodiment 〉
Then second embodiment to the inventive method describes.
Fig. 5 is the flow chart of operation of second embodiment of expression the inventive method.This second embodiment is that between step S3 in Fig. 3 and the step S4, design has the step S3-1 of the operation of reoxidizing with the difference of first embodiment that illustrates based on Fig. 3.In this case, carry out the modification operation by these two operations of the modified process that reoxidizes operation and step S4 of this step S3-1.
Specifically, finish, then this wafer W is transferred load to from CVD processing unit 16C and reoxidize processing unit 16D (with reference to Fig. 1), carry out reoxidizing processing (S3-1) as the feature of the inventive method if the highly dielectric thin film among the step S3 forms operation.
This reoxidizes processing unit 16D and forms structure shown in Figure 2, makes to be O in the container handling 24 2Gas atmosphere makes the wafer W rotation of mounting on the mounting table 26, simultaneously by 58 pairs of wafer surface irradiation ultraviolet radiations of ultra-violet lamp.This ultraviolet ray is preferably based on the ultraviolet ray of wavelength 172nm.This point is common item in the 3rd～the 7th each embodiment after this.
In this case, be not cut off the temperature of the oxygen key in the highly dielectric thin film 4 as the treatment temperature of chip temperature, for example be below 500 ℃, preferably heating maintains about 450 ℃.
In addition, processing pressure at this moment for example in the scope of 2.6～133Pa, preferably in the scope of 2.6～65Pa, is suitably adjusted the ultraviolet decay based on oxygen.This point is common item in the 3rd～the 7th each embodiment after this.In addition, the processing time for example is about 15～180sec also based on the thickness of highly dielectric thin film 4.
Like this at O 2Produce oxygen radical by irradiation ultraviolet radiation under the existence of gas, the oxygen radical of this generation is invaded in the highly dielectric thin film 4 and is reoxidized, the damaged part of oxygen in can repair membrane.That is, under the state that forms highly dielectric thin film 4, do not wish in this film, to have the damaged part of oxygen,, can repair the damaged part of above-mentioned oxygen by oxygen radical thus, thereby can correspondingly improve membranous so carry out the above-mentioned processing that reoxidizes.
In addition, by this O 2Ultraviolet irradiation in the gas atmosphere can be removed organic components remaining in the highly dielectric thin film 4, particularly can remove carbon component, and film carries out shrink fit and becomes firm.Consequently, the film density of highly dielectric thin film 4 improves, by densification, so can prevent damaged generation, keeps the high-k state.And, can suppress SiO as basilar memebrane 2 2The increase of the thickness of film.Such O 2The effect of the ultraviolet irradiation in the gas atmosphere also is common item in the 3rd～the 7th each embodiment after this.
In addition, carrying out under this situation that reoxidizes processing, oxygen radical penetrates highly dielectric thin film 4 when arriving it with the interface of silicon substrate side, at this interface portion formation SiO 2Film makes basilar memebrane 2 become thicker.Therefore, in order to prevent such situation, the treatment conditions when this is reoxidized processing are set at the condition that oxygen radical can not penetrate highly dielectric thin film 4.Such treatment conditions are, for example pressure is about 2.67Pa, and the time is about 15sec.
Like this, finish, then transfer to next step S4, carry out above-mentioned modified process and operation after this if reoxidize operation.
Under the situation of this second embodiment, not only can bring into play the action effect same with the first previous embodiment, and as mentioned above, the oxygen that can repair highly dielectric thin film 4 is damaged, further improves membranous, simultaneously can reduce concentration of carbon, carry out shrink fit film density is improved.
＜the three embodiment 〉
Then the third embodiment of the present invention is described.
Fig. 6 represents the flow chart of operation of the 3rd embodiment of the inventive method.
The 3rd embodiment only is that the step that will reoxidize operation is labeled as S4-1 with the order transposing of the modified process that reoxidizes operation and step S4 of the step S3-1 of second embodiment shown in Figure 5.
The situation of the 3rd embodiment not only can be brought into play the action effect same with the first previous embodiment, and with second embodiment similarly, the oxygen that can repair highly dielectric thin film 4 is damaged, further improves membranous, simultaneously can reduce concentration of carbon, carry out shrink fit film density is improved.
In addition, think in the modified process of step S4, in Ar atmosphere during to highly dielectric thin film 4 irradiation ultraviolet radiations, to be subjected to by the high UV-induced damage of energy oxygen taking place damaged owing to this film surface, therefore, shown in the 3rd embodiment, after this modified process, implement to reoxidize the modification processing of operation again, then can reoxidizing operation by this, to repair above-mentioned oxygen damaged, thereby can correspondingly further improve membranous.
＜the four embodiment 〉
Then the fourth embodiment of the present invention is described.
Fig. 7 is the flow chart of operation of the 4th embodiment of expression the inventive method.
As shown in Figure 7, the 4th embodiment is the abridged flow process that the basilar memebrane that do not carry out the step S2 of second embodiment shown in Figure 5 forms operation, and the highly dielectric thin film of directly transferring to step S3 from the pretreatment procedure of step S1 forms operation.After this each operation is identical with the situation of second embodiment.But,,,, make the oxygen radical that produces can penetrate the condition enactment of highly dielectric thin film 4 herein in order to form basilar memebrane as the treatment conditions that reoxidize in the operation.Such treatment conditions are, for example pressure is about 2.67Pa, and the time is about 60sec.
In the 4th embodiment, form operation because omit basilar memebrane as mentioned above, so come not form basilar memebrane 2 (with reference to Figure 15) outwardly.But, in fact carry out step S3-1 reoxidize operation the time, by at O 2Irradiation ultraviolet radiation under the existence of gas and the oxygen radical that produces are invaded and are reoxidized in the highly dielectric thin film 4, the part that oxygen in the repair membrane is damaged, and the oxygen radical of a part penetrates in this highly dielectric thin film 4 boundary that arrives with the surface of silicon substrate, consequently, make silicon oxidation, form by SiO herein 2The basilar memebrane 2 that constitutes.That is, under the situation of the 4th embodiment, after lamination forms highly dielectric thin film 4, at its interface formation basilar memebrane 2 with silicon substrate.Like this, in the 4th embodiment, reoxidize operation except having the damaged effect of original reparation oxygen, also have the effect that forms basilar memebrane.
Under the situation of the 4th embodiment, not only can bring into play the action effect same with the second previous embodiment, can also reduce concentration of carbon, carry out shrink fit and improve film density.In addition, form operation because omit the basilar memebrane of step S2, so can correspondingly improve production capacity.
＜the five embodiment 〉
Then the fifth embodiment of the present invention is described.
Fig. 8 is the flow chart of operation of the 5th embodiment of expression the inventive method.
As shown in Figure 8, the 5th embodiment is the abridged flow process that the basilar memebrane that do not carry out the step S2 of the 3rd embodiment shown in Figure 6 forms operation, and the highly dielectric thin film of directly transferring to step S3 from the pretreatment procedure of step S1 forms operation.This point is identical with the 4th previous embodiment.And each operation after this is identical with the situation of the 3rd embodiment.But,,, make the oxygen radical that produces can penetrate the condition enactment of highly dielectric thin film 4 in order to form basilar memebrane herein as the treatment conditions that reoxidize in the operation.Such treatment conditions are, for example pressure is about 2.67Pa, and the time is about 60sec.
In the 5th embodiment, form operation because omit basilar memebrane as mentioned above, thus identical with the situation of previous the 4th embodiment, come not form basilar memebrane 2 (with reference to Figure 15) outwardly.But, in fact carry out step S4-1 reoxidize operation the time, by at O 2Irradiation ultraviolet radiation under the existence of gas and the oxygen radical that produces are invaded and are reoxidized in the highly dielectric thin film 4, the part that oxygen in the repair membrane is damaged, and the oxygen radical of a part penetrates in this highly dielectric thin film 4, arrive the boundary on the surface of itself and silicon substrate, consequently, make silicon oxidation, form by SiO herein 2The basilar memebrane 2 that constitutes.That is, under the situation of the 5th embodiment, after lamination forms highly dielectric thin film 4, at its interface formation basilar memebrane 2 with silicon substrate.Like this, in the 5th embodiment, reoxidize operation and not only have the damaged repair of original oxygen, also have the effect that forms basilar memebrane.
Under the situation of the 5th embodiment, not only can bring into play the action effect same, can also reduce concentration of carbon, carry out shrink fit and improve film density with the 3rd previous embodiment.In addition, form operation because omit the basilar memebrane of step S2, so can correspondingly improve production capacity.
＜the six embodiment 〉
Then the 6th embodiment to the inventive method describes.
Fig. 9 is the flow chart of operation of the 6th embodiment of expression the inventive method.
As shown in Figure 9, the 6th embodiment, in the modified process of the step S4 of first embodiment shown in Figure 3, will be in irradiation ultraviolet radiation gas supplied change from Ar gas (non-active gas) and be oxygen (O 2) gas, other each operation is identical with the situation of first embodiment.
Shown in the 6th embodiment, in the modified process here, make in the container handling 24 is not non-active gas atmosphere but oxygen atmosphere, make the wafer W rotation of mounting on the mounting table 26, and to the wafer surface irradiation ultraviolet radiation, carry out modification processing at the highly dielectric thin film 4 (with reference to Figure 15) of wafer surface formation by ultra-violet lamp 58.
The processing pressure here is for example in the scope of 2.6～133Pa, preferably in the scope of 2.6～65Pa.In addition, treatment temperature is identical with the situation of first embodiment, and the low temperature of the oxygen key in not cutting off above-mentioned highly dielectric thin film 4 for example carries out under the temperature below 500 ℃.And, consider preferably treatment temperature to be set at the efficient of modification about 450 ℃.In addition, the processing time is about 15～180sec also according to the thickness of highly dielectric thin film 4.Compare with the situation of previous first embodiment, this processing time is wanted much shorter.
Handle by this modification, identical with the situation of previous first embodiment, make organic components remaining in the highly dielectric thin film 4, particularly carbon component breaks away from, and film carries out shrink fit and becomes firm.Consequently, because the film density of highly dielectric thin film 4 improves, densification,, keep the high-k state so can prevent damaged generation.Because can improve the membranous of highly dielectric thin film 4 like this, so can make its electrical characteristics good.
In addition, in the 6th embodiment, the oxygen radical that produces by ultraviolet irradiation is invaded in the highly dielectric thin film 4 and is reoxidized, and the damaged part of oxygen in can repair membrane for example can have the function that reoxidizes operation that illustrates concurrently in second embodiment etc.
, experimentize, to aforesaid O herein 2Ultraviolet irradiation (UV-O in the atmosphere 2) the validity handled of modification estimate, its evaluation result is described.
Figure 10 is expression ultraviolet irradiation and the atmosphere gas chart to the influence of the concentration of carbon of highly dielectric thin film.And measure density, thickness, the roughness (surface roughness) of highly dielectric thin film, the results are shown in down in the tabulation 2.Wherein, this is measured and uses XRR (X ray reflection rate method).
[table 2]
Figure A20068004831200211
From above-mentioned table 2 as can be known, about the density of film, at UV-O 2Under the situation of irradiation from the 4.48g/cm of initial value 3Significantly increase to 4.71g/cm 3, can confirm UV-O 2Irradiation can make film density significantly increase.
In addition about thickness, at UV-O 23.32nm from initial value under the situation of irradiation significantly is thinned to 3.24nm, can confirm UV-O 2Can make significantly attenuation of thickness under the situation of irradiation.
About roughness, compare almost not variation in addition, can confirm not produce any problem with initial value.
In Figure 10, represented the state of the sample test portion that is made among the figure, roughly the same with situation about in Fig. 4 B, representing, on silicon substrate, thickness with 10nm forms the two-layer highly dielectric thin film that is made of HfSiO respectively, and the highly dielectric thin film of lower floor is under Ar atmosphere or O 2Carry out 30 minutes UV irradiation under the atmosphere, the highly dielectric thin film on upper strata does not carry out the UV irradiation.In addition, heating-up temperature is set at 450 ℃.And, as depth direction, measure concentration of carbon by SIMS with the thickness direction of this two-layer highly dielectric thin film.X among the figure, Y are equivalent to the thickness of each layer.
Characteristic C represents the situation of the UV irradiation in the Ar atmosphere, and characteristic D represents O 2The situation of the UV irradiation in the atmosphere.Herein, the irradiation time under the situation of the UV irradiation in the Ar atmosphere is 30 minutes, and is relative therewith, O 2Irradiation time under the situation of the UV irradiation in the atmosphere is 1 minute.From this chart as can be known, the part of region-of-interest Y, the O that characteristic D is represented 2In the situation of UV in atmosphere irradiation, though irradiation time only be very short 1 minute, concentration of carbon with the represented Ar atmosphere of characteristic C in the UV situation mode identical or below it of shining reduce.Therefore can confirm, if utilize O 2The modification of the UV irradiation in the atmosphere is handled, and then can obtain desirable effect in the short time, thereby can help improving production capacity.
＜the seven embodiment 〉
Then the seventh embodiment of the present invention is described.
Figure 11 is the flow chart of operation of the 7th embodiment of expression the inventive method.
As shown in figure 11, the 7th embodiment is the abridged flow process that the basilar memebrane that do not carry out the step S2 of the 6th embodiment shown in Figure 10 forms operation, same with the 4th embodiment that represents in Fig. 7, the highly dielectric thin film of directly transferring to step S3 from the pretreatment procedure of step S1 forms operation.After this each operation is identical with the situation of the 6th embodiment.
In the 7th embodiment, form operation because omit basilar memebrane as mentioned above, thus same with the 4th previous embodiment, come not form basilar memebrane 2 (with reference to Figure 15) outwardly.But, when in fact in step S4, carrying out modified process, by at O 2Irradiation ultraviolet radiation under the existence of gas and the oxygen radical that produces are invaded and are reoxidized in the highly dielectric thin film 4, the part that oxygen in the repair membrane is damaged, and the oxygen radical of a part penetrates in this highly dielectric thin film 4 boundary on the surface that arrives itself and silicon substrate, consequently, make silicon oxidation, form by SiO herein 2The basilar memebrane 2 that constitutes.That is, under the situation of the 7th embodiment, after lamination forms highly dielectric thin film 4, at its interface formation basilar memebrane 2 with silicon substrate.Like this, in the 7th embodiment, modified process is except effect with original reduction concentration of carbon and film is carried out also have the effect of repairing the damaged effect of oxygen and forming basilar memebrane the effect of shrink fit.
Under the situation of the 7th embodiment, not only can bring into play the action effect same with the 6th previous embodiment, also form operation, so can correspondingly improve production capacity because omitted the basilar memebrane of step S2.
And, in the various embodiments described above, after the modification of highly dielectric thin film is handled, must carry out nitrogen treatment at last, but this nitrogenize operation also can be carried out before handling being about to carry out above-mentioned modification, and in addition, this nitrogenize operation itself can not carried out yet and is omitted.
＜UV-O 2The evaluation that processing and UV-Ar handle 〉
Then, the O in the various embodiments described above, carrying out 2Ultraviolet irradiation operation in the atmosphere (below be also referred to as " UV-O 2Handle "), the effect of the ultraviolet irradiation operation in non-active gas (Ar) atmosphere (below be also referred to as " UV-Ar processing ") is described in more detail.
Figure 12 is the chart of the relation of expression EOT and grid leakage current.Herein, the UV-O to carrying out representing among above-mentioned second～the 7th embodiment 2Situation about handling and the situation of not carrying out are estimated respectively, and in order to compare, also the result of the existing oxygen radical that utilizes plasma when handling carried out in expression.In addition, the change processing time is carried out UV-O three times 2Handle.Wherein, EOT is with by as the HfSiO film of highly dielectric thin film and the SiO of basilar memebrane 2The lamination of film and the electric capacity of the gate insulating film that forms is converted into single S iO 2The value of thickness.In addition, in ultraviolet irradiation, utilize excited quasi-molecular lampbulb, use the ultraviolet ray as main body, in addition UV-O with wavelength 172nm 2Processing pressure during processing is set at below the 65Pa, does not produce the ultraviolet decay that is caused by oxygen as far as possible.These main points also are identical in Figure 13 and situation shown in Figure 14.
As can be seen from Figure 12, utilize in the modification that the plasma oxygen radical handles existing, grid leakage current is quite a lot of, and EOT is significantly increased.Relative therewith, can confirm carrying out UV-O 2Under the situation about handling, the processing time is long more, more can the suppressor grid leakage current.Its reason is to pass through UV-O 2Processing reduces concentration of carbon, and it is damaged to have repaired oxygen.But about EOT, it increases gradually along with the growth in processing time, becomes not wish the result that obtains.In addition, under the situation that existing plasma oxygen radical is handled, can not control concentration of oxygen free radicals, it can become too high and make the SiO of basilar memebrane 2Thickness increases, and makes the EOT of gate insulating film significantly increase, but at UV-O of the present invention 2Under the situation about handling, by adjusting ultraviolet intensity, O 2Dividing potential drop can be adjusted concentration of oxygen free radicals, can control the increase of EOT.
Some is related for the situation of Figure 13 and Figure 12, is expression UV-O 2Handle (wavelength: 172nm) with the chart of the relation of EOT and trap density.Here in order to compare, also record the result under the situation of existing plasma oxygen radical jointly.Figure 13 A represents UV-O 2The relation of processing time and EOT, Figure 13 B represents UV-O 2The relation of processing time and trap density.Make UV-O herein, 2Processing time changes between 0～90sec.The processing time that existing in addition plasma oxygen radical is handled is 10sec.Wherein, UV-O 2Processing time is that 0sec is meant certainly and does not implement UV-O 2Handle.
As shown in FIG. 13A, under the situation of existing plasma oxygen radical, the recruitment H1 of thickness (is benchmark with 0sec) is very big, is judged to be not wish situation about occurring.Relative therewith, carrying out UV-O 2Under the situation about handling, the processing time increases, and EOT just little by little increases, even but the processing time be 90sec, with respect to about original thickness 1.32nm, its recruitment H 2Below 0.1nm, compare with existing plasma oxygen radical processing, can significantly suppress the increase of EOT.
In addition, shown in Figure 13 B, about trap density, in existing plasma oxygen radical is handled, 2.5 * 10 11Cm -2About be extraordinary.Relative therewith, for UV-O 2Handle, this processing time is long more, and trap density will reduce gradually and become good, when proceeding to the 90sec left and right sides, can confirm to become the roughly the same value of handling with existing plasma oxygen radical of situation.The reason that reduces along with the increase in processing time of trap density is like this, carbon is broken away from and during densification, also makes trap break away from the damaged minimizing of oxygen simultaneously in the process along with the processing time.
Above-mentioned Figure 13 A and Figure 13 B are the relations that balance is selected, therefore in the processing of reality, according to as the EOT of target, at random determine above-mentioned UV-O as the trap density of target 2Processing time.Figure 14 is expression UV-O 2The chart of the influence that handle, UV-Ar handles etc. causes the relation of flat band voltage (Vfb) and trap density.Wherein, ultraviolet wavelength uses the wavelength as main body with 172nm.
Above-mentioned flat band voltage (Vfb) is corresponding with the amount of the fixed charge that gate insulating film is had, and this fixed charge influences transistorized threshold voltage.Trap density and flat band voltage are not independently to concern, both have the represented dependency relation with straight line M1 in the formation method of existing gate insulating film.
In general transistorized manufacturing process, the annealing in process operation after forming, gate insulating film is arranged, exist with ... this processing time, trap density reduced successively when the processing time was elongated, and flat band voltage also shifts to zero direction explicitly therewith.
Herein, clearly distinguished without the group A of above-mentioned annealing in process operation and the group B of annealed treatment process.In above-mentioned group of A, enumerate and only carry out UV-O 2Handle the situation X1 of (60sec) and only carry out these two examples of situation X2 that UV-Ar handles.Among this external group of B, the situation Y1 that any UV handles is not carried out in expression respectively, only carries out the situation Y2 that UV-Ar handles and will change into 15sec, 60sec, 90sec the processing time respectively and only carry out UV-O 2Situation Z1, the Z2, the Z3 that handle.
In the formation method of existing gate insulating film, trap density and flat band voltage exist with ... above-mentioned annealing in process, only can carry out by the adjustment of the dependency relation of straight line M1 restriction.
Relative therewith, the arrangement separately of situation X1, the X2 in the group A and situation Y1, Y2 in the group B, Z1～Z3 is the direction along longitudinal axis almost parallel.In other words, in each group A, B, can make flat band voltage Vfb only optionally change trap density hardly as can be known with changing.That is, irrelevant with above-mentioned annealing in process operation, by carrying out UV-O 2Processing, UV-Ar handle, and can make flat band voltage Vfb only optionally control the factor of trap density hardly with changing.
＜variation 〉
In the various embodiments described above, be illustrated as example as the situation of refractory metal with the main Hf of use (hafnium), but be not limited thereto, also can use Ta (tantalum), Ti (titanium), W (tungsten), Zr (zirconium) etc., with the silicide (silicate) of its oxide or its oxide as highly dielectric thin film.
In this case, the above-mentioned organo-metallic compound material that contains tantalum can use and be selected from tertbutylimido three (diethylin) tantalum (TBTDET): [(NEt 2) 3TaN-Bu t], five (ethylmethylamino) tantalum (PEMAT): [Ta (NMeEt) 5], five (dimethylamino) tantalum (PDMAT): [Ta (NMe 2) 5], five (diethylin) tantalum (PDEAT): [Ta (NEt 2) 6], tertbutylimido three (ethylmethylamino) tantalum (TBTMET): [(NEt 2Me) 3TaN-Bu t], tertiary pentyl imino group three (dimethylamino) tantalum (TBTDMT): [(NMe 2) 3TaN-Bu t], tertiary pentyl imino group three (dimethylamino) tantalum (Taimata, trade name): [(NMe 2) 3TaNC (CH 3) 2C 2H 5] (Ta (Nt-Am) (NMe 2) 3) in a kind of material.
The above-mentioned organo-metallic compound material that contains titanium can use and be selected from four (diethylin) titanium Ti[N (C 2H 5) 2] 4, four (dimethylamino) titanium Ti[N (CH 3) 2] 4, four (ethylmethylamino) titanium Ti[N (CH 3) (C 2H 5)] 4In a kind of material.
The above-mentioned organo-metallic compound material that contains tungsten can use and be selected from tungsten carbonyl W (CO) 6, two (uncle's fourth imino group) two (dimethylamino) tungsten (t-Bu tN) 2(Me 2N) 2A kind of material among the W.
In addition, illustrated here, but be not limited thereto, in glass substrate, LCD substrate, ceramic substrate etc., also can use the present invention with the example of semiconductor wafer as handled object.

Claims (20)

1. the method for modifying of a highly dielectric thin film, this highly dielectric thin film use organo-metallic compound material, are formed on the surface of handled object, and this method of modifying is characterised in that, comprising:
Preparation is formed with the preparatory process of the described handled object of described highly dielectric thin film from the teeth outwards; With
Keep described handled object the regulation temperature, and in the atmosphere of non-active gas to described highly dielectric thin film irradiation ultraviolet radiation, carry out the modified process of the modification of described highly dielectric thin film thus.
2. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that, also comprises:
Reoxidize operation, it is the operation of carrying out before being about to carry out described modified process, keep described handled object the regulation temperature, and in the atmosphere of oxygen to described highly dielectric thin film irradiation ultraviolet radiation, the oxygen of repairing thus in the described highly dielectric thin film is damaged.
3. the method for modifying of highly dielectric thin film according to claim 2 is characterized in that:
In the atmosphere of described oxygen to the processing pressure in the operation of described highly dielectric thin film irradiation ultraviolet radiation in the scope of 2.6～65Pa.
4. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that, also comprises:
Reoxidize operation, it is the operation that and then described modified process carries out, keep described handled object the regulation temperature, and in the atmosphere of oxygen to described highly dielectric thin film irradiation ultraviolet radiation, the oxygen of repairing thus in the described highly dielectric thin film is damaged.
5. the method for modifying of highly dielectric thin film according to claim 4 is characterized in that:
In the atmosphere of described oxygen to the processing pressure in the operation of described highly dielectric thin film irradiation ultraviolet radiation in the scope of 2.6～65Pa.
6. the method for modifying of a highly dielectric thin film, this highly dielectric thin film use organo-metallic compound material, are formed on the surface of handled object, and this method of modifying is characterised in that, comprising:
Preparation is formed with the preparatory process of the described handled object of described highly dielectric thin film from the teeth outwards; With
Keep described handled object the regulation temperature, and in the atmosphere of oxygen to described highly dielectric thin film irradiation ultraviolet radiation, carry out the modified process of the modification of described highly dielectric thin film thus.
7. the method for modifying of highly dielectric thin film according to claim 6 is characterized in that:
In the atmosphere of described oxygen to the processing pressure in the operation of described highly dielectric thin film irradiation ultraviolet radiation in the scope of 2.6～65Pa.
8. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
Described ultraviolet ray is the ultraviolet ray of wavelength based on 172mm.
9. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
In the lower floor of described highly dielectric thin film, be formed with by the SiO that forms by oxidation processes 2The basilar memebrane that film constitutes.
10. the method for modifying of highly dielectric thin film according to claim 9 is characterized in that:
Described basilar memebrane forms by form the basilar memebrane formation operation of carrying out before the operation at the highly dielectric thin film that forms described highly dielectric thin film on the surface of handled object.
11. the method for modifying of highly dielectric thin film according to claim 9 is characterized in that:
Described basilar memebrane forms when carrying out described modified process simultaneously.
12. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
The temperature of the regulation in the described modified process is not cut off the temperature of the oxygen key of described highly dielectric thin film.
13. the method for modifying of highly dielectric thin film according to claim 12 is characterized in that:
The temperature of the regulation in the described modified process is below 500 ℃.
14. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
Described highly dielectric thin film is made of the oxide of refractory metal or the silicate of this oxide.
15. the method for modifying of highly dielectric thin film according to claim 14 is characterized in that:
Described refractory metal is any among Hf, Ta, Ti, W, the Zr.
16. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
After described modified process, be used for the nitrogenize operation on the surface of the described highly dielectric thin film of nitrogenize.
17. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
Before described modified process, be used for the nitrogenize operation on the surface of the described highly dielectric thin film of nitrogenize.
18. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
Described highly dielectric thin film is transistorized gate insulating film.
19. the method for modifying of highly dielectric thin film according to claim 1 is characterized in that:
Described non-active gas is N 2, among He, Ar, Ne, Kr, the Xe arbitrarily more than one.
20. a semiconductor device is characterized in that:
Comprise that the highly dielectric thin film that is modified by the described method of modifying of claim 1 is as gate insulating film.
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